Synthesis of stable and soluble one-handed helical poly(substituted acetylene)s without chiral pendant groups via polymer reaction in membrane state

A soluble and stable one-handed helical conjugated polymer without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer having two hydroxyl groups followed by desubstitution of the chiral groups in a solid membrane state. The reason for the success was the polymer reaction was carried out in the membrane state. This is an alternative method to obtain such a unique chiral polymer which was obtained only by the helix-sense-selective polymerization (HSSP) we reported before. In addition the efficiency of the chiral induction was higher than that of the HSSP. It is interesting that the “Membrane state” acted like as if a protecting group.     

Preparation of Co–Mo/B2O3/Al2O3 catalysts for hydrodesulfurization: Effect of citric acid addition

The effect of citric acid (CA) addition was studied on the HDS of thiophene over Co–Mo/(B)/Al₂O₃ catalysts. The catalysts were characterized by means of LRS, Mo K-edge EXAFS, NO adsorption capacity measurements, and UV–vis spectra. The catalysts were subjected to a chemical vapor deposition (CVD) technique using Co(CO)₃NO as a precursor of Co in order to get deeper insights into the effect of citric acid addition. It was shown that the HDS activity was enhanced by the citric acid addition up to the CA/Mo mole ratio of around 1 and leveled off with further addition. The amount of Co anchored by the CVD was increased by the addition of citric acid, suggesting an increase in the dispersion of MoS₂ particles on the catalyst by the simultaneous presence of Co, Mo and citric acid, in conformity with the increase in the NO adsorption capacity. In contrast to Co–Mo catalysts, the edge dispersion of MoS₂ particles in Mo/B/Al₂O₃ was not affected by the addition of citric acid. The LRS, UV–vis spectra and Mo K-edge EXAFS showed that Co–CA and Mo–CA surface complexes are formed by the addition of citric acid. The Co–CA surface complex is more preferentially formed on CoMo/Al than on CoMo/B/Al, in agreement with a greater promoting effect of citric acid at a lower CA/Mo mole ratio for CoMo/Al than for CoMo/B/Al.     

Direct Observation of Pure Cu and Cu-Ag Anode Passivation in H2SO4-CuSO4 Aqueous Solution by Channel Flow Double Electrode and Optical Microscopy

Metallurgical and Materials Transactions B - The dissolution and passivation of pure Cu and Cu-5 wt pct Ag anodes in H2SO4-CuSO4 electrolyte were investigated by a direct...     

Mechanical properties of cross-ply and quasi-isotropic composite laminates processed using aligned multi-walled carbon nanotube/epoxy prepreg

This study examined the processing and mechanical properties of cross-ply and quasi-isotropic composite laminates processed using aligned multi-walled carbon nanotube/epoxy prepreg sheets. Three kinds of CNT/epoxy laminates, ([0°/90°]s, [60°/0°/?60°]s, [0°/45°/90°/?45°]s) were successfully fabricated using aligned CNT/epoxy prepreg sheets. The CNT volume fraction was approximately 10%. No visible void or delamination was observed in composite laminates, and the thickness of each layer was almost equal to that of the prepreg. To evaluate the elastic moduli, E₁₁, E₂₂, and G₁₂, of each ply in the laminates, on-axis and off-axis tensile tests (0°, 45°, 90°) were conducted of aligned CNT/epoxy lamina specimens. The Young’s modulus of CNT/epoxy cross-ply and quasi-isotropic laminates agreed with the theoretical values, which were calculated using classical laminate theory and elastic moduli of CNT/epoxy lamina. The respective failure strains of [0°/90°]s, [60°/0°/?60°]s, and [0°/45°/90°/?45°]s laminates are 0.65, 0.92, 0.63%, which are higher than that of 0° composite lamina (0.5%). Results suggest that the failure strain of 0° layer in composite laminates is improved because of the other layers.     

Cartesian-structure analysis in cast films by advanced infrared multiple-angle incidence resolution spectroscopy

Multiple-angle incidence resolution spectroscopy (MAIRS) has been improved to be an advanced algorithm so that the Cartesian structure in organic thin films can be analyzed. The infrared MAIRS technique was originally proposed as a totally new spectroscopic technique to reveal structural anisotropy in thin films on an infrared-transparent substrate, which yields both in-plane- (IP; X and Y) and out-of-plane (OP; Z)-mode spectra from an identical sample. Since this technique employs an analytical concept based on a signal decomposition of light intensity (not absorbance spectra), the algorithm intrinsically has high potential for further development. In the present study, the theoretically deduced matrix that correlates the light intensity to the angle of incidence has been modified to further decompose the IP-mode spectrum into X and Y components. As a result, anisotropic measurements of infrared spectra of thin film have become possible for the X, Y, and Z directions (Cartesian coordinate) simultaneously. With this advanced algorithm, the Cartesian structural changes in a cast film prepared on a germanium substrate have readily been analyzed, and a change from the biaxial to the uniaxial film structure with aging has spectroscopically been revealed.     

Measuring cosmic-ray exposure in aircraft using real-time personal dosemeters

Aircrew exposure to radiation was measured on several long-haul flights using two small commercial electronic personal dosemeters: one was a photon dosemeter, the NRF20; the other was a neutron dosemeter, the NRY21-both manufactured by Fuji Electric Systems Co. Ltd. for radiation protection at nuclear facilities. Non-neutron doses were measured using the photon dosemeter, and neutron doses were measured using the neutron dosemeter. The measured non-neutron doses at commercial aviation altitudes agree with the EPCARD (European Program Package for the Calculation of Aviation Route Doses) dose calculation within a difference of 8 %. However, the recorded neutron doses were 5-15 times larger than the EPCARD calculation. These over-measurements are dependent on cut-off rigidities.     

The microwave effect on the properties of silica-coated TiO2 fine particles prepared using sol-gel method

The silica coating of TiO₂ fine particle was conducted using microwave assisted sol-gel method and conventional sol-gel method to suppress its photo-catalytic activity. The amount and uniformity of silica coating on TiO₂ surface were characterized by X-ray photoelectron spectroscopy (XPS), X-ray fluorescence spectroscopy (XRF), infrared spectroscopy (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and zeta potential measurements. XPS and XRF results showed that the presence of catalyst and reaction time were important factors to reach high silica amounts. SEM, TEM, and zeta potential results indicated that dense film coating of SiO₂ layer formed on TiO₂ surface in conventional sol-gel method, whereas the nucleation coating was observed on sample prepared by microwave assisted sol-gel method. When photo-catalytic activities and ultraviolet (UV) shielding abilities of these samples were evaluated, the sample prepared by microwave processing showed higher inhibition of photo-catalytic activity and better UV shielding ability than the sample prepared by conventional method. These results suggested that the coating method significantly affected the photo-catalytic activity and UV shielding ability of coated TiO₂.     

The study of metal ion release and cytotoxicity in Co–Cr–Mo and Ti–Al–V alloy in total knee prosthesis – scanning electron microscopic observation

We surgically retrieved two cobalt(Co)–chromium(Cr)–molybdenum(Mo) and five titanium(Ti)–aluminum(Al)–vanadium(V) alloy knee prostheses from patients because of mechanical failure and pain. We examined the distribution of the small particles which were released from the Co–Cr–Mo and Ti–Al–V alloys using a backscattered scanning electron microscopy (SEM). In addition we analyzed the metals in the artificial knee joints and the tissues adjacent to them using energy dispersive X-ray spectroscopy (EDS). We demonstrated that a myriad of fine particles, produced by the abrasion of both Co–Cr–Mo and Ti–Al–V alloys, accumulated in the synovial cells. As Co–Cr–Mo alloys disintegrate easily in the cells, Co dissolves from the peripheral areas of them, although Cr remains within the cells. In contrast Ti–Al–V alloys are very stable in the synovial cells. From these findings we conclude that the Co–Cr–Mo alloys are hazardous to the body as the alloys release Co which enters the body. In contrast the Ti–Al–V alloys are very stable and are patently safer. Artificial joints, however, are still in considerable need of improvement.     

Mechanistic study on analyte focusing by dynamic pH junction in capillary electrophoresis using computer simulation

Dynamic pH junction is an on-line preconcentration method in capillary electrophoresis (CE) based on electrokinetic focusing of weakly ionic analytes with in large sample volumes in a multisection electrolyte system. In this report, experiments and computer simulations were performed to gain a better insight of the analyte focusing mechanism when a dynamic pH junction was used. A computer program, SIMUL, was used to simulate the band-narrowing process of a group for phenol derivatives under optimized buffer conditions, which were compared with experimental results. Computer simulations revealed the formation of a sharp moving pH boundary within the sample zone causing efficient focusing of long plugs of weakly acidic analytes based on their pKa. These studies offered useful information for understanding the band-narrowing process by control of the depth and lifetime of the moving pH boundary as a function of analyte pKa, sample pH, and injection length. The change in pH of the sample within the capillary was also estimated by measuring the absorbances of an analyte at two different wave-lengths. Optimization of analyte focusing resulted in enhanced detection responses of about 60-450-fold in terms of peak heights for some phenol derivatives' relation to conventional injections. Dynamic pH junction represents a novel approach to control band dispersion (peak width) and selectivity (mobility) of specific analytes for high-resolution CE separations.     

Earth‐Abundant and Durable Nanoporous Catalyst for Exhaust‐Gas Conversion

Precious metals (Pt and Pd) and rare earth elements (Ce in the form of CeO₂) are typical materials for heterogeneous exhaust‐gas catalysts in automotive systems. However, their limited resources and high market‐driven prices are principal issues in realizing the path toward a more sustainable society. In this regard, herein, a nanoporous NiCuMnO catalyst, which is both abundant and durable, is synthesized by one‐step free dealloying. The catalyst thus developed exhibits catalytic activity and durability for NO reduction and CO oxidation. Microstructure characterization indicates a distinct structural feature: catalytically active Cu/CuO regions are tangled with a stable nanoporous NiMnO network after activation. The results obtained by in situ transmission electron microscopy during NO reduction clearly capture the unique reaction‐induced self‐transformation of the nanostructure. This finding can possibly pave the way for the design of new catalysts for the conversion of exhaust gas based on the element strategy.